HU224200B1 - Flame-retardant and fabric-softening treatment of textile materials - Google Patents

Abstract

A one-pack composition conferring flame-retardant and fabric-softening properties on fabrics comprises a THP<+> salt, an organic nitrogen compound (eg urea) and a hydroxyl-reactive organic compound having 12 or more carbon atoms. Preferred examples of such compounds include C12 amine, C18 amine and tallow amine (viz a C16 / C18 / C20 amine mixture).

Description

(54) Refractory and softening treatment of textile materials (57) Extract

FIELD OF THE INVENTION The present invention relates to compositions for fire retardant and fabric softening compositions comprising a THP ⁺ salt, an organic nitrogen compound (such as urea) and a hydroxyl reactive organic compound having 12 or more carbon atoms. Preferred examples of such compounds include C 12 amines, C 18 amines and tallow amine (namely, a C ₁₆ / C ₁₈ C ₂₀ amine mixture).

The invention also relates to tissues treated with the above compositions and to the preparation of the above compositions.

HU 224 200 Β1

The scope of the description is 6 pages

HU 224 200 Β1

The present invention relates to a composition having a refractory property and a softening effect to textile materials, to a process for the preparation of the above composition and to a textile material treated with the composition.

Known process for impregnating textile materials, including cellulose (e.g., cotton) fibers, with a poly (hydroxy-organic) -phosphonium compound, such as an aqueous solution of tetrakis (hydroxy-organic) -phosphonium (THP ⁺ ) salt, to impregnate these materials available. Alternatively, the polyhydroxy-organophosphonium compound may contain condensate with a nitrogen-containing compound, such as urea. After impregnation, the fabric is dried and crosslinked with ammonia to form a mechanically fixed, crosslinked, water insoluble polymer in the fibers of the fabric. After crosslinking, the polymer is oxidized to convert trivalent phosphorus to pentavalent phosphorus, and the fabric is washed and dried. Textiles treated as described above and clothing made from such treated textiles are marketed by Albright & Wilson Limited under the TRADE name.

GB-A-2271787 discloses the addition of one or more protonated and neutralized amines (e.g., amine acetates) to the impregnating solution. Such dosing has been found to increase the efficiency of the anchoring of phosphonium compounds in fibers, which in turn has been found to result in improved fire resistance and increased water repellency.

According to the solution described in FR 2 304 712, an organic compound containing (a) a tetrakis (hydroxymethyl) phosphonium sulfate (THPS), (b) a trivalent amine bearing methylol and / or alkylated methylol groups and (c) ) a wetting agent is used. These ingredients are applied to the fabric to be made refractory by a process involving impregnation, drying and heat curing.

GB 1 435 296 discloses a process for making refractory materials containing organic fiber, preferably polyester, which comprises: (i) condensation products of tetrakis (hydroxymethyl) phosphonium compounds with self-condensation or reactive nitrogen compounds, ( (ii) a soft tactile agent which is a nitrogenous compound and (iii) a water soluble amino-1,3,5-triazine is used as a treatment reagent.

GB-A-2040299 (Albright & Wilson Limited) mentions the addition of an inorganic base or a C 1 -C 4 tertiary amine base to a THP ⁺ compound prior to condensation with urea. However, the aforementioned GB-A-2040299 does not mention the softness (soft fall) of the textile material treated with the product of the disclosure.

Our co-pending GB 9412484.9 discloses a process for the preparation of a

To increase the application of THP ^{+ to the} textile material, resulting in improved refractory properties.

It has been found that adding a primary or secondary aliphatic amine having 12 or more carbon atoms prior to reacting the reactants to condense the THP ⁺ salt and the organic nitrogen compound with an aqueous mixture of a THP ⁺ salt and an organic nitrogen compound, leading to the formation of a composition which, when used to treat textiles by the aforementioned PROBAN process, not only provides the fabric with refractory properties, but also has improved fabric softening properties.

Accordingly, the present invention relates to a composition which imparts fire resistance to and softens textile materials, which composition is (a) a tetrakis (hydroxy-organic) -phosphonium salt (THP ⁺ ), (b) an organic nitrogen compound, and (c) product of the reaction of an aliphatic hydroxyl reactive compound having 12 or more carbon atoms.

The invention also relates to textile materials treated with the composition described in the preceding paragraph.

The present invention further provides a process for preparing a composition as described above, comprising (i) adding a THP ⁺ salt (a) to a container and adjusting its pH to about 6.0 by addition of an inorganic base;

(ii) dissolving the organic nitrogen compound (b) in the THP ⁺ salt / base solution;

(iii) adding (c) to [(a) + (b) j;

(iv) maintaining the mixture of [(a) + (b) + (c) j at a suitable temperature for such time as to form a condensation product between (a) and (b);

(v) cooling the product; and (vi) adding sufficient water to the product to form a stable solution.

The invention further relates to a composition prepared by the process described in the preceding paragraph.

Preferably, the THP ⁺ salt of component (a) is a tetrakis (hydroxyalkyl) phosphonium salt such as tetrakis (hydroxymethyl) phosphonium chloride (THPC) or tetrakis (hydroxymethyl) phosphonium sulfate (THPS). ).

The organic nitrogen compound serving as component (b) is preferably an amide such as urea or thiourea.

Component (c) may be, for example, one or more of the following compounds (each containing at least one alkyl group having 12 carbon atoms or more):

(i) primary amines (ii) secondary amines (iii) tertiary amines (iv) quaternary ammonium salts (vi) ethoxylated amines (vii) ethoxylated diamines (viii) amine oxides (ix) alkylamino-substituted carboxylic acids ( x) amides

EN 224 200 Β1 (xi) ethoxylated amides (xii) amidoimidazolines (xiii) siloxane derivatives (xiv) silane derivatives.

When the compound of the component (C) an amine, for example, may consist essentially of n-dodecyl amine (C ₁₂ H ₂₅ NH ₂₎ or n-octadecyl amine (C ₁₈ H ₃₇ NH _2).

Alternatively, the compound serving as component (c) may be a tallow amine, which is assumed to be n-hexadecylamine (C ₁₆ H ₃₃ NH ₂ ), n-octadecyl amine (C ₁₈ H ₃₇ NH ₂ ) and n-eicosyl. containing an amine (C ₂ H _{4 2} NH ₂ ).

The molar ratio of the THP ⁺ salt to component (a) to the sum of the molar ratios of organic nitrogen compound to component (b) to compound (c), i.e., from: 4: 1 to 1.5: 1 (b + c) 2.5: 1 to 3: 1.

For example, the molar ratio a: b: c could be:

4: 0.95: 0.05

3.5: 0.95: 0.05

3: 0.95: 0.05

2.5: 0.95: 0.05

2.5: 0.9: 0.1

2.5: 0.75: 0.25

2.0: 0.95: 0.05

2: 0.9: 0.1 or 1.5: 0.95: 0.05

The textile material may consist essentially of 100% cellulosic fibers (e.g., cotton, canvas, jute, hemp or regenerated cellulose).

Alternatively, the textile material may comprise cellulosic fibers and non-cellulosic fibers simultaneously. Non-cellulosic fibers may be, for example, wool or silk fibers, or they may contain synthetic fibers, such as polyester, polyamide, acrylic or aramid fibers.

Preferably, the textile material comprises cellulosic fibers (e.g., cotton) or may comprise cotton fibers and polyester fibers, such as 60% cotton fiber and 40% polyester fiber.

The inorganic base used in step (i) of the process of the invention may be, for example, sodium hydroxide or potassium hydroxide.

In step (iv) of the process, for example, the mixture can be kept at reflux for 3-4 hours. This step can be carried out at or above atmospheric pressure, for example about 1.25 x 10 ⁵ Pa.

In step (vi) of the process of the invention, enough water is added to obtain a 60% stable solution.

While not wishing to be bound by any particular theory, it is believed that adjusting the pH of the THP ⁺ salt to about 6.0 will render the salt more reactive with the organic nitrogen compound. It is also believed that the detectable softer feel (drop) of the treated textile material is due in part to the reduced crosslinking of the THP ⁺ salt / compound (c) and / or to the presence of compound (c) in the chain. It is further believed that the treatment of textile materials according to the invention leads to improved tensile strength and wear resistance.

The invention will now be illustrated by the following examples.

Example 1

1400 g of tetrakis (hydroxymethyl) phosphonium chloride (THPC) is charged into a 2 liter resin flask equipped with a reflux condenser. The pH is adjusted to about 6 by addition of 75 g of 50% potassium hydroxide solution. 132 g of urea were introduced into the resin vessel and dissolved with stirring.

Subsequently, 38 g of n-octadecylamine (marketed as ARMEEN * HTD) are added to the vessel and the mixture is brought to reflux. The mixture is refluxed for 3-4 hours until the amine disappears, then the heating is stopped and water is added to make a 60% solution.

The molar ratio of THPC: urea to n-octadecylamine is 2.5: 0.95: 0.05.

280 g / m ² of 100% cotton wool is impregnated with the above liquid to a 40% PROGAN * weight gain and processed by the known PROBAN * procedure. The dry weight gain of the fabric product with the condensation product is 18.5%.

The fabric treated with the above liquid has a content of 2.75% P and 2.38% N, and after 40 cycles of washing at 93 ° C, satisfies German (a), French (b) and British (c) FR tests.

Notes to Example 1:

* ARMEEN and TRIAL are registered trademarks.

(a) DIN 66083 s-b (b) NFG 07-184 (c) BS 6249

2-6. examples

The procedure described in Example 1 was followed, but the amounts given in Table 1 were used and the results given therein were obtained.

Table 1

The number of the example (a) THPC (g) 50% KOH (g) (b) Urea (g) (c) Amine (g) molar ratio (ABC) Dry Weight Growth (%) In processed tissue P (%) N (%) Second 1190 60 108 * 48 2.5: 0.75: 0.25 17.6 2.6 2.25 Third 1428 75 171 * 36 2: 0.95: 0.25 19 2.77 2.55

HU 224 200 Β1

Table 1 (continued)

The number of the example (A) THPC (g) 50% KOH (9) (b) Urea (g) (c) Amine (g) molar ratio (ABC) Dry Weight Growth (%) In processed tissue P (%) N (%) 4th 1190 60 108 * 48 2.5: 0.9: 0.1 17.6 2.6 2.25 5th 1428 75 162 * 72 2: 0.9: 0.1 19 2.6 2.44 6th 1190 101 108 18,5+ 2.5: 0.9: 0.1 - 2.96 2.52

* n-octadecylamine + n-dodecylamine

2-6. Each of the tissues obtained in Examples 1 to 4 meets the requirements of the fire resistance tests described in Example 1.

7-10. examples

Again, the same procedure as in Example 1 is followed, but these examples only illustrate the preparation of refractory compositions, not their use on textile materials. The quantities used shall be those shown in Table 2.

Table.

Table 2

The number of the example (A) THPC (g) 50% KOH (g) (b) Urea (g) (c) Amine (g) Molecular gold (a: b: c) Comment 7th 1190 60 95 20 3: 0.95: 0.05 8th 1190 60 71 15 4: 0.95: 0.05 9th 1190 60 81.4 17 3.5: 0.95: 0.05 10th 1074 60 171 36 1.5: 0.95: 0.05 Forms a polymer gel

1-6 above. The tissues treated with the products of Examples 1 to 4 are substantially better in texture and fall than those treated with the composition disclosed in the aforementioned GB-A-2040299.

11-15. examples

The procedure is as described in Example 1, using a molar ratio of THPC: urea to amine of 3: 0.95: 0.05 and the pressure, temperature and time values given in Table 3.

Table 3

The number of the example Temperature (° C) Pressure (bar) Time (minutes) 11th 105-108 Atmospheric 180 12th 110 0.5 150 13th 130 1.25 20 14th 130 1.25 20 15th 130 1.25 20

^One hundred percent cotton fabric weighing 280 g / m ^{2 is} treated with the product described above. The treated fabric has a phosphorus and nitrogen content of 3% and 2.5%, respectively, after 40 washes at 93 ° C, meeting the requirements of German, French, British and new European Pr EN 533 fire resistance tests.

16-20. examples

The procedure described in Example 11 was followed using the tissues shown in Table 4.

Table 4

The number of the example Fabric composition (%) structure zet Weight of tissue (g / m ² ) Cotton PET * 16th 100 0 twill 280 17th 100 0 Smooth 155 18th 100 (színnyc 0 rmásos) Smooth 185 19th 75 25 twill 255 20th 65 35 twill 280

The treated fabrics meet the requirements of German, French, British and the new European Pr EN 533 fire resistance standards after the required durability washes.

* PET = poly (ethylene terephthalate)

Table 5 shows the phosphorus and nitrogen contents measured before and after the endurance washes.

HU 224 200 Β1

Table 5

The number of the example P & N% Content (Finished) P & N% content (after washing) P% N% P% N% 16th 3.05 2.46 2.84 2.26 17th 4.55 3.65 - _ * 18th 2.98 2.45 2.10 1.63 19th 3.02 2.46 3.01 2.24 20th 3.49 2.81 2.97 2.42

In addition, the fabrics are excellent to the touch and fall. In addition, blended fabrics are water repellent.

* A17. In Example 1, the fabric was subjected to 200 durations of washing at 74 ° C with an oxidant-free detergent. The tissue has a phosphorus content of 2.80% and a nitrogen content of 2.21% after the above treatment and is in compliance with BS 5867 Part 2, Type B test.

Claims (18)

A composition having a fire resistance and fabric softening properties to a textile material, characterized in that (a) a tetrakis (hydroxy-organic) phosphonium salt (THP) salt, (b) an organic nitrogen compound, and (c) a 12 or a reaction product of an aliphatic hydroxyl reactive compound with a higher carbon atom, wherein the molar ratio of the THP ⁺ salt of component (a) to the sum of the molar ratios of organic nitrogen compound of component (b) to amine of component (c), ie: (b + c) = (4) , 0-2.0): 1, and a: b: c molar ratio (4.0-2.0) :( 0.95-0.75) :( 0.25-0.05). The composition of claim 1, wherein the THP ⁺ salt of component (a) is a tetrakis (hydroxyalkyl) phosphonium salt, such as tetrakis (hydroxymethyl) phosphonium chloride (THPC) or tetrakis (hydroxymethyl) phosphonium sulfate (THPS). Composition according to claim 1 or 2, characterized in that the organic nitrogen compound as component (b) is an amide such as urea or thiourea. 4. A composition according to any one of claims 1 to 3, wherein the compound as component (c) is a primary amine, a secondary amine, a diamine, a quaternary ammonium salt, an ethoxylated amine, an ethoxylated diamine, an amine oxide, an alkylamino-substituted carboxylic acid, an amide, an ethoxylated amide, an amidoimidazoline, a siloxane or a silane derivative. The composition of claim 4, wherein the compound as component (c) is essentially n-dodecylamine (C ₁₂ H ₂₅ NH ₂ ). 6. The composition of claim 4, wherein the compound in component (c) consists essentially of n-octadecylamine (C ₁₈ H ₃₇ NH _2). The composition of claim 4, wherein the compound of component (c) is n-hexadecylamine (C ₁₆ H ₃₃ NH ₂ ), n-octadecylamine (C ₁₈ H ₃₇ NH ₂ ) and n-eicosyl. -amine (C ₂₀ H ₄₁ NH ₂ ). The composition of claim 1, wherein the a: b: c molar ratio is 3.5: 0.95: 0.05, 3: 0.95: 0.05, 2.5: 0.95: 0.05, 2.5: 0.9: 0.1, 2.5: 0.75: 0.25, 2.0: 0.95: 0.05, 2.0: 0.9: 0, 1 or 1.5: 0.95: 0.05. 9. Textile material, characterized in that according to claims 1-8. A composition according to any one of claims 1 to 6. A textile material according to claim 9, characterized in that it consists essentially of 100% cellulose fiber. 11. The textile material of claim 10, wherein said fibers are cotton fibers, canvas fibers, jute fibers, hemp fibers or regenerated cellulosic material. 12. A textile material according to claim 9, characterized in that it consists of cotton, wool or silk fibers. 13. A textile material according to claim 9, characterized in that it consists of cotton fibers and synthetic fibers, such as polyester, polyamide, acrylic or aramid fibers. 14. A textile material according to claim 13, characterized in that it comprises 60% by weight of cotton fiber and 40% by weight of polyester fiber. 15. Procedure 1-8. Compositions according to any one of claims 1 to 3, characterized in that: (i) adding the THP ⁺ salt (a) to a container and adjusting its pH to about 6.0 by addition of an inorganic base; (ii) dissolving the organic nitrogen compound (b) in the THP ⁺ salt / base solution; (iii) adding (c) to the [(a) + (b)] mixture; wherein the compounds serving as components (a), (b) and (c) are represented by a: (b + c) = (4.0-2.0): 1 and a: b: c = (4.0-2, 0) :( 0.95-0.75) :( 0.25-0.05) molar ratios are used; (iv) maintaining the mixture of [(a) + (b) + (c) j at 80 to 120 ° C for 1.5 to 8 hours to form the condensation product between (a) and (b); (v) cooling the product; and (vi) adding sufficient water to the product to form a stable solution. 16. A process according to claim 15 wherein the inorganic base in step (i) is sodium hydroxide or potassium hydroxide. The process according to claim 15 or 16, wherein in step (iv) the mixture is maintained at reflux for 3-4 hours. Process according to claim 15, 16 or 17, characterized in that in step (vi) sufficient water is added to obtain a 60% stable solution.